Note: Descriptions are shown in the official language in which they were submitted.
GC76
The present invention relates to washing compositions
and to processes for washing.
Conventionally ~ashing compositlons contain ir~ addition
to a surfactant, an alka]i builder salt, which amongst other
S functions, imparts to solutions of the washing composition
an alkaline pH, and removes from solution or in some way
neutralises the effect of alkaline earth metal ions such as
calcium and magnesium which could interfere with or otherwise
render less efficient the utilisation of the surfactant.
Conventionally, the builder salt has been an alkali metal
phosphate, commonly sodium tripolyphosphate. However, in
recent years, the problem of eutrophication in inland waterways
has become apparent to an increasing extent. It is believed
that phosphates contribute significantly to eutrophication, and
that a signlficant proportion of the phosphate arises as a
result of its incorporation in washing compositions.
Accordingly, therefore, considerable efforts have been made to
davelop washing compositions having a substantially reduced
phosphate content. Of the many substitutes that have been
proposed for phosphates, one class which has the advantage of
being produced from readily available materials is that of
zeolites. Generally, zeolites having a general composition
in the ranges xNa20:A1203:ySiO2 where x is from 0.7 to 1.5
and y is from 0.8 to 6.0 have been proposed, but the zeolite
that is normally selected from that range is Zeolite 4~. Now,
Zeolite 4A is relatively efficient at removing calcium ions
- 2 -
~ .
GC76
~14 ~ ~
.. . ..
from solution, and we have confirmed that it is relatively
inefficient at removing magnesium ions from solution. Both
magnesium and calcium contribute to the total hardness of
the water.
It is an object of at least some embodiments of the
present invention to provide a washing composition which
contains a zeolite and which has an improved capability
for removing the magnesium from the solution than doe~
zeolite 4A.
According to the present invention there is provided a
washing composition containing at least one surfactant,
zeolite 13X and zeolite 4A and optionally containing one or
more of the other components which can be included in
washing compositions.
. .
Zeolite 13X, advantageously, as far as we are aware, not
only can remove calcium from ~olution at a rate comparable to
that of Zeolite 4A during the initial period of, e.g. one
minute, when the washing composition is ~rought into contact
with the liquor, but also can remove magnesiuM from solution
more quickly and to a greater extent than does Zeol te 4A.
Zeolite 13X is characterised by a mole ratio of xNa20:
A1203:ySiO2 wherein x is from 0.8 to 1.2 and y is from 2.4 to
3.0, and zeolite 4A by xNa20:A1203:ySiO2 wherein x is from 0.8
to 1.2 and y is from 1.35 to 2.35 and both, in practice, normally
contain water of hydration. I`he x-ray diffraction pattern of a
typical zeolite 13X is described in USP 3013990 column 2 lines
28 to 62, and that of zeolite 4A in USP 2882243 column 8 line
69 to column 11 line 18. Zeolites 13X and 4A must not be
confused with any other zeolites having a mole ratio of soda
-- 3
. :
- ~ :
.
.:
G~76
'f'3~
to alumina to silica within the ranges described hereinbefore
with respect to zeolite 13X or 4A but which do not have the
characteristic x-ray diffraction patterns of zeolite 13 X or 4A.
Such other zeolites do not form part of the present invention.
l'he suprising and unexpe?ted nature of the present
invention can be seen by examLning the capacity of various
zeolites to remove calcium from solution. Now, even though
2eolite A has a much smaller window than Zeolite Y its
capacity for removing calcium from solution is substantially
better than that of Zeolite Y. On the other hand, Zeolite
13X having a similar window to Zeolite Y is substantially
as good as Zeolite 4A, at least initially, whereas synthetic
mordenite, a alumino silicate having a very high silica to
alumina mole ratio and an even larger window is worse even
than Zeolite Y. Thus, it will be seen that there is no
simple relationship between, for example, window size and
calcium removal capability. ;~hen the magnesium removal
capability of the same zeolites is tested, it becomes
immediately apparent that Zeolite 4A and mordenite are
behaving substantially similarly, with mordenite beiny
arguably better, and that Zeolite Y can remove magnesium to a
limited extent whilst Zeolite 13X is more than twice as good as
any of the other zeolites tested. It will thus be seen that
whilst Zeolite 4~ was arguably the best at removiny calcium
it was arguably the worst at removing magnesium. A
comparison of the calcium removing and magnesium removing
capabilities of the various zeolites emphasises the surprising
and unexpected nature of the present invention, and in
particular that a knowledge of the window size and calcium
GC76
t rA ~ 13
removing capa~it~ give., no i.ndication of the rnaynesium
removing capacity of a zeolite.
Desirably, the properties of ï3x and 4A in the washing
compositions fall within the range of from 90:10 to 20:80,
proportions herein being ~y weight of anhydrous zeolite unless
otherwise stated. Within suc~ a r~nge, the proportion
of calcium ions removed from solution appear to be
substantially the same as that of zeolite 4A, whilst the
proportion of rr.a~nesium removed from solution appears to
be markedly better than that cf 2eolite 4A. Moreover,
within this range, the proportion of magnesium ions
removed is generally greater than would be expected by
ir,terpolation along a straight line graph from 100% for4A
to 100% 13X. Although the effect of high concentrations of
sodium salts including builders, is to tend to compress the
difference in magnesium removing capability between 4A and
13X, synergism between 13X and 4A in the aforementioned
range of 90:10 to 20:80 is stlll readily observable. Also,
there is some indication that wit~n this range, the
calcium removing capability of the mixture might also be
slightly better than that of ~A or 13X by themselves,
especially at the lower end of the range, that is to say
where the proportion of 4A in the mixture is from 2G to 33~.
In preferred embodiments, 13X represents at least
50% of the mixture of 13X and 4A. Such a mixture is
substantially better than 4A alone and is nearly as good as 13X
by itself for removing magnesium, whilst retaining very
good calcium removing propert~es, so that the mixture
exhibits great versatility in its use, in that it can
-- 5
GC76
cope with water supplies havirg only a small proportion
of the hardness in the form of magnesium salts right up
to waters in which a substantial or major proportion of
hardness is caused by magnesium salts. This is to be
contrasted with 4A by itself, whose performance falls
off significantly as the propGrtion of magnesium ions
forming the hardness increases. In especially desirable
embodiments, the proportion of 13X in the 13X/4A mixture
is at least 65% and preferably is not more than 85%. Within
the ran~e of 65% to 85%, and ~specially at 75% + 3%, the total
hardness removal can often be at or close to the rnaximum in this
range when at least 20% of the total hardness is caused
.... ~
by magnebium. Even when the proportion of total hardness
attributable to the magnesium is less than 20~, the
mixture is substantially as good as solely 4A at calcium
removal, so that the mixture is suitable for such waters
also. It will be seen, therefore, that the benefit of
using a mixture of 13X and 4A, namely that of achieving
optimal total hardness removal from waters containing
a high proportion of magnesium,does not lead to significant
or substantial impairment of performance for waters having
only a low magnesium content.
In practice, washing compositions according to the
present invention can contain between 5 and 95% by weight of
13X/4A, preferably between 10 and 70~ by weight. It will
be recognised that the 13X/4A mixture is intended as a partial
or full replacement for phosphates and that in general the 13X/4A
mixture can be used in approximately the same or possibly
slightly hi~her proportions in washing compositions as
-- 6
GC76
phosphate.s couki r~e u~ n~ t~iat in ~Ictorr(li~iny tllo
proportion, the int~nded u.;~ the wa~ihlrl-~ colnposition and
how much othe.r bullder .~alt l~j present will norlnally be
taken into accoun-t. Also, ev(~n withln a broadly accepted
term like he~vy duty washlny composltlon the normal ranges
of proportion of bullder in the composition can very widely
from country to country, e~g. often bei~y in the range of
10 to 40% in the U.K., but up to 70% in Germany. The
washing compositio~s are rlot Lestricted to heavy duty
washing compositions but can l~e compositions formulated
for any given purpose which could alternati.vely contain
phosphates as builder salt. .,uch compositions include light
duty household washing composltions, machine washing powders
and scouring powders, in addition to heavy duty general
household washing compositions or those formulated for
automatic washing machines.
In practice, it is preferable for both of the zeolites
to have a particle size of less than 45~, preferably less
than 30~ and particularly in -the range of 0.1 to lO~.
It will be recognised that the benefit of reducing
eutrophication caused by phosphates rises as the proportion
of phosphate replaced by zeol:,,tes in the detergent builder
mixture rises. However, we have surprisingly found a
synergistic effect when a mixture of zeolites 13X and 4A is
employed together with sodium tripolyphosphate (STPP) in a
weight ratio of total zeolite to STPP in the range of 95:5
to 40:60. Such a synergistic effect appears to be absent
when either of zeolites 13X or 4A alone is used together
GC7
with STPP in a ~eight ratio in the same range. The
synergistic effect is more pronounced when the proportion
of 13X in the mixture of æeolites 13X and 4A falls within
the preferred range of from at least 50~ up to 85% w~w
and more preferably from 65 to 85~ w/w.
~e have also found that by incorporating a minor amount,
e~g. up to 5.0~ by weight of certain complexing agents in such
composi~ions, their performance in washing fabrics can be improved.
Consequently, in some highly desirable embodiments,
the washiny composition contains a mixture of Zeolites
13X and 4A together with a minor amount of a complexing
agent selected from (a) glassy phosphates, (b) poly(alpha-
hydroxy acrylic acid) and alkali metal salts thereof, and
(c) ethylenea~ine (methylenepnosphonic acids) and alkali metal
salts thereof.
According to a further aspect of the present invention,
there is provided a builder composition suitable for
incorporation in a detergent composition comprising zeolites
13X and 4A and a complexing agent selected from (a) glassy
phosphates, (b) poly(alpha-hydroxyacrylic acid) alkali metal
salts thereof, and (c)ethyleneamine(methylenephosphonic acids)
and alkali metal salts thereo
Herein, by the term "glassy phosphates" are meant
compounds of formula M4P207(~'03)n~ wherein M represents an
alkali metal cation, preferably sodium, and n is at least 2.
Preferably detergent compositions according to the present
invention contain from 0.1 to 4~.0~ by weight of the glassy
phosphate, and especially at ~east 0.5% by weight.
GC76
1~4~
It will h~ reco~nised that the terrn"ethylenearnine
(methylenepho~L~honic acids/" inclicates that the compounds
are analogous to ethyleneamine carboxylic acids, methylene-
phosphonic acid groups replacing acetic acid groups.
Examples of this class of compound are diethylenetriamine-
penta (methylenephosphonic acid) and ethylenediaminetetra-
(methylenephosphonic acid). Such a compound can be used
in the acid for~ or as an alkali metal salt thereof,
suitably sodium or potassium salt. Preferably, a detergent
composition according to the present invention contains
from 0.1 to 4.0% by weight of either an ethyleneamine
(methylenephosphonic acid) or its salt or poly(alpha-hydroxy
acrylic acid) or its salt, or both. Thus, in particularly
preferred embodiments, detergent compositions contain from
0.5 to 4.0% by weight glassy phosphate and from 0.5 to 4.0%
by weight of a compound in class (b) and/or a compound in
class (c).
The ratio of 13X and 4A can be in the range of 90:10
to 20:80, preferably at least 50:50 and especially desirably
in the range of 65:35 to 85:15, when the composition contains a
compound in classes (a), (b), or (c).
In addition to the aforementioned components, the
composition contains preferably from 0.1 to 4.0~ of one or
more of classes (a), (b) and (c) herein described. In some
especially desired embodiments, the detergent composition
contains not only a compound in class (a) but also a compound
in class (c) to a total amount of (a) and (c) of from 1
to 5% by weight. Especially desirably, the compound in
class (c) is diethylenetriaminepenta (methylenephosphonic acid)
., ' , ' ~, ,
.: ~
, : . - . .
, : :. , :-
:-
. ,
GC76
L~
or its alkali metal salt.
One way of forming washing compositions as described
hereinbefore is to first form a premix of the detergent
builder components whlch is then mixed with the remainder
of the components in one or more stages to form the desired
washing composition. Thus~ a deteryent builder composition
according to the present invention can suitably comprise
from 1 to 10% by weight of one or more of components (a),
(b) and (c) and the remainder a mixture of zeolites 13X and
4A. Especially desirable builder compositions comprise
from 1 to 10~ of component (a), from 1 to 10% of either
component (b) or component (c) or a mixture of components
(b) and (c), and from 98 to 80~ of the mixed zeolites
13X and 4A. It will be recognised that the formation of
a washing composition containing from 10 to 40~ by weight
of said builder composition aforementioned inevitably
contains from 0.1 to 4.0% by weight of one or more of classes
(a), (b) and (c). However, if it is desired to use greater
than 40% builder composltion in the washing composition,
it will be further recognised that the maximum amount of
any of classes (a), (b) and (c) in the builder composition
will decrease as the proportion of builder composition in
the washing composition increases. Thus, for example, if
the washing composition is to contain 60% builder composition
then the maximum proportion of class (a) in the builder
composition is 6.7~ to give 4% in the washing composition.
, .. ...
Preferably, the proportion of any of classes (a), (b) and (c),
when present in the builder composition is between 3 and 7% by
_ 10
.
GC76
L~a7.~P J;~J
weight. Tnus, preferred builder compositions comprise from 3
to 7~ of class ~a), from 3 to 7~ of class (~) or (c) or a
.. .. .. .. .. _ . ,
mixture of (b) and (c) and from 94 to 86% of a mixture of
zeolites 13X and 4A. An especially ~esirable builder
composition comprises from 3 to 7% of class (a), from 3
to 7% of class (c) and from 94 to 86~ of a mixture of
zeolites 13X and 4A. The amount of class (a) can be matched
with the amount of class (b) or class (c) or a mixture of
classes (b) and (c). It will be understood that in the
builder composition, the mixture of Zeolites 13X and 4A
is suitably that ratio desired in the washing composition,
so that in practice, the ratio is preferably in the range
of 65:35 to 85:15 for 13X:4A.
Other Components of the Washin~ Compositions
In addition to one or more detergent builders as described
hereinbefore the washing compositions according to the
present invention contain a surfactant (otherwise referred
to interchangeably as surface active agent or tenside or
tencio active agent) as described herein normally in an
2~ amount of from 5 to 95% and in many embodiments from 5 to 25
and preferably from 8 to 14~ by weight of the washing
composition. Other phosphate-free detergent builders
described hereinafter can also be included, normally in an
amount of not more than 50~ of the washing composition, and
often in the range of O to 10% of the washing composition,
or together with any STPP,forming up to half the total weight
of builder salt in the washing composition. The composition
can also contain, if desired, a solid organic or inorganic
-- 11 --
GC76
71~ ~
active oxygen-containing compound, desirably in an amount
of from 0 to 40% by weight, and preferably from 10 to 30
by weight, together if desired with one or more bleach
activators. The composition can also include a filler or
processing aid such as sodium sulphate suitably in an
amount of fronl 0 to 40% by weight and auxiliary agents in
a total amount of from 1 to 20% by weight of the washing
composition, such auxiliary agents being known in themselves
and include soil anti-redeposition agents, dye transfer
inhibitors, optical brighteners,enzymes, stabilisers,
corrosion inhibitors, bactericides, dyes, perfumes, foam
inhibitors, absorbents and abrasives.
Surfactants
The surfactants which can be employed in washing
compositions according to the ~resent invention can be
non-ionic, anionic, cationic, or amphoteric. Generally,
the surfactants contain at lea3t one hydrophobic group,
e.g. an aliphatic hydrocarbon ~roup containing at least 8
carbon atoms, and often from 1~ to 26 carbon atoms, the
aliphatic group often being ac~clic, but sometimes containing
an alicycllc group, or the hydrophobic group can be an
alkaryl group containing at least six and preferably up
to 18 allphatic carbon atoms. The surfactant contains in
addition at least one water solublising group for example
a sulphonate, sulphate or carboxylic group which is linked
either directly or indirectly to the hydrophobic group.
Linking members can include residues of polyhydric alcohols
containing etheric or esteric Linkages, for example derived
GC76
;_
~$l4~1sD
from ethylene ylycol, propylen~ glycol, glycerine or
polyether residues. The surfactants can be soap or be
synthetic, for example as described in chapter 2 of
Synthetic Detergents by A Davi~sohn and B M Milwidsky,
5th Edition published in 1972 by Leonard Hill, London, and
methods of making them are described in chapter 4 of the
same book.
Amongst anionic surfactants described on pages 15-23
of the aforementioned book, sulphonates and sulphates are
of special practical importanc~. The sulphonates include,
for example, alkaryl sulphonat~s, and particularly alkyl
benzene sulphonates, the alkyl group preferably being
straight chain containing 9 to 15 carbon atoms, of which
one of the most commonly emploved is linear dodecyl benzene
-15 sulphonate. Other sulphonates which are useful as anionic
surfactants include olefin sulphonates, obtained, for
example, by sulphonating primary or secondary aliphatic
mono-olefins, alkene sulphonates, especially linear alkene
sulphonates, and hydroxy alken~ sulphonates and disulphonates,
especially 3-,4-, and 5-,hydroxy-n-alkyl sulphonates in
which the alkyl group contains any even number from 10
to 24 carbon atoms. Other desirable anionic surfactants
include alcohol sulphates, preferably linear, having a
chain length of at least 10 carbon atoms and sulphated
fatty acid alkanolamides. Other sulphates comprise
sulphated nonionic surfactants as for example alkylphenyl-
ethylene oxide ether sulphate in which the alkyl groups
contain from about 8 to 12 carbon atoms and there are 1 to
- '' ' '' '' ': :
.. ....
, , . ~ .'. '.' ' - ' ~' ,
,
: . :
. . ..
GC76
, .--~ ~ .
4~
10 units of ethylene oxide in each molecule. Yet other
sulphate sur~actants comprise alkyl ethyl sulphates where
the alkyl group contains from 10 to 20 carbon atoms,
preferably linearly and each molecule contains from 1 to
10 preferably from 1 to 4 molecules of ethylene oxide.
It is not generally intended that cationic detergents
be present in the same composition as anionic surfactants,
but when cationic detergents are used they are frequently
quaternary ammonium salts such as tetraalkyl ammonium
halides in which at least one of the alkyl group contains
at least 10 carbon atoms or quaternary pyridinium salts
substituted by an alkyl chain of at least 10 carbon atoms.
A considerable proportion of nonionic surfactants
suitable for use in the present invention comprise
condensation products of ethylene oxide and possibly
propylene oxide. One class of such nonionic surfactants
which is of special importance comprises water soluble
condensation products of alcohols containing from C8 to
C18 with an ethylene oxide polymer often containing at
least 10 molecules of ethylene oxide per molecule of
surfactant, e.g. from 10 to 30 moles of ethylene oxide.
Particularly desirable nonionic surfactants comprise
water soluble condensates of alkyl phenols or alkyl
naphthols with an ethylene oxide polymer normally
containing from 5 to 25 moles of ethylene oxide per mole
of alkyl phenol or alkyl naphtnol. The alkyl group
- 14
.
GC76
.~
normally contains frol~ 6 to 12 carbon atoms and is
frequently nonionic.
As an alternative to the hydrophobic moiety of the
nonionic surfactant being linked to the hydrophilic moiety
by an ether link as in alkyl phenol ethylene oxide
condensates, the linkage can be an ester group. The
hydrophobic moiety is normally the residue of a straight
chain aliphatlc acid containing from 10 to 22 carbon atoms
and more particularly lauric, stearic and oleic residues.
In one classof nonionic ester surfactants, the hydrophilic
moiety comprises polyethylene oxide, frequently in the
ratlo of from 5 to 30 moles of ethylene oxide per ~ole of
the fatty acid residue. It will be recognised that both
mono and di esters can be employed. Alternatively it is
possible to employ as the hydrophilic moiety glycerol,
thereby producing either mono or di glycerides. In a
further group, the hydrophilic moiety comprises sorbitol.
A further class of nonionic surfactants comprice
alkanolamides in which a C10 to C22 amide is condensed
2~ with a polyethylene oxide or polypropylene glycol hydrophilic
moiety or moieties. Semi-polar detergents include
water soluble amine oxides, water soluble phosphene oxidss
and water soluble sulphur oxides, each containing one alkyl
moiety of from 10 to 22 carbon atoms and two short chain
~5 moieties selec*ed from the groups of alkyl and hydroxyalkyl
groups containing 1 to 3 carbon atoms. -
Amphoteric surfactants in~lude derivatives of aliphatic
-- 15
-
' - ' . ' - .:
, .
-,
. ~
GC76
~ ~.................................................................... . i
~ 147~
quatenary ammonium, sulponium and phosphonium compounds
in which the alipha~c moieties can be linear or branched,
or two of which can join to form a cyclic compound,
provided that at least one of the constituents comprises
or contains a hydrophobic group containing from about 8
to 22 carbon atoms and the compound also contains an
anionic water solùbilising group, often selected from
carboxylic, sulphate and sulphonates.
Other builders which can be included can be inorganic
compounds for example alkalimetal silicates, carbonates,
blcarbonates, or borates or they can be organic, as for
example alkali metal salts of ethyleneaminepolycarboxyliC
acid, polyhydroxyacrylic acid, of acids like citric acid
or gluconiç acid.
The inorganic active oxygen-containing compound is
normally selected from sodium }~erborate tetrahydrate or
monohydrate, the addition product of sodium caEbonate and
hydrogen peroxide, commonly re~erred to in commerce as
sodium percarbonate, and similarly sodium perpyrophosphate, and
sodium pertripolyphosphate and alkali metal and ammonium
persulphates. The organic actlve oxygen-containing compound
is normally selected from the class of solid mono or di-
peroxy acids such as mono or di- perazaleic, diperoxyisophthalic
acld, diperoxyterephthalic acid, 4-chlorodiperoxyterephthalic
acid, or allphatlc peroxy aclds contalnlng 10 to 20 carbon
atoms alpha substituted by a sulphonate group, or alkali
metal, preferably sodium, salts of any of them. Other
sultabla organic active oxygen-containing compounds include
'
- 16 -
.
.
. ~ . . ~ . ' ' :
.
' ', ', .
.
, '. ' ' ' , ;' ' ~ '
GC76
solid organic peroxides such as benzoyl glutaryl peroxide,
. . __ . .
diphthaloyl peroxide and its hydrogenated equivalents, and
solid diacyl peroxides derived from any of the afore-
mentioned peroxy acids. It will be recognised that the
diacyl peroxides function not only as active oxygen-
containing compounds in their own right, but can also
function as a bleach activator in that by reaction with
hydrogen peroxide produced from a solid inorganic compound
in solution such as sodium perborate tetrahydrate or
sodium percarbonate, a second peroxy acid species is
produced from each molecule of diacyl peroxide. The invention
composition can also contain any solid bleach acti~ator as
proposed hitherto, mainly of the N-acyl or 0-acyl compounds.
Compounds which are typical of the class of bleach activator
lS whlch they represent include N,N,N',N',-tetraacetyl-
methylenediamine, or the corresponding ethylenediamine
compound, which are typical of n-diacylated alkyl or alkalene
amines; benzoic or phthalic annydride; tetraacetylglycoluril,
which is typlcal of acylated glycolurils. The aforementioned
bleach activators are of ~articular importance, but others
which can be employed fall within the class of N-alkyl-N-
sulphonyl-carbonamides, N-acyl hydantoins, carbonic acid
esters, triacylcyanurates, 0,N,N'-tri substituted
hydroxylamine~ such as 0-Benzoyl-N,N-succinyl-hydroxylamine,
N,N'-diacyl-sulphuryamides and 1,3-diacyl-4,5-diacyloxy-
imidazolldlnes.
The auxlliary agents which can be incorporated in
compositions accordlng to the present invention include
- 17
, - . : -, : .
, . . . . .
- - - - . :. . .. :, ,. : ~ ..
.: - :
, : . . : , ..
.. : : .
- .
GC76
the auxiliary agents in the classes specified hereinbefore
which have been disclosed for incorporation in phosphate-
containing compositions. By way of example, sodium
carboxymethylcellulose is of practical importance as a soil
anti redeposition agent and derivatiYes of diaminostilbene-
sulphonic acid, diarylpyrazolines and aminocoumarins are
incorporated for brightening cotton and polyamide fabrics.
One convenient method of producing particulate
solid compositions according to the present invention
comprises the steps of first forming a paste or suspension
of all the components of the composition with the exception
of any active oxygen-containing compound and activator
therefor, normally employing water, and thereafter
converting the paste or suspension to the solid state by
hot drying suitably at a temperature in the range of
100 to 250C, preferably by spray drying, thereby forming
a particulate solid material which in a later stage can
be mixed or blended with the particulate active oxygen-
containing compound and bleach activator, if any. In
. . ~
alternative methods of preparation, tw~ or more pastes or
suspensions could be formed, each containing one or more of
the spray-driable components and dried separately, if desired.
Thus, e.g. a suspension of all or part of the zeolites
together if desired with any other builders, could first be
formed and dried in the manner previously described and a
second aqueous paste, suspension, or solution could be formed
containing the surfactant and the residue of the builders and
any other components (except the oxygen-containing component
- 18
- .... . ..... ' ' ' ', - ' -' .
- . . - .: .
GC76
and activator therefor1 which is separately dried as before,
and then the various components are blended together in the
solid state. Alternatively, a part of the sur~actant may
be incorporated in the builder composition that is
separately dried. In a further alternative, where the
surfactant is nonionic, all or part of the surfactant may
be incorporated into or coated on the surface of the
active oxygen-containing compound, especially when it is
highly porous such as sodium perborate monohydrate, the
proportion incorporated in this manner being no more than
the proportion at which a reasonably free flowing product
remains.
In use, washing composltions according to the present
invention are dispersed or dissolved in a washing medium,
lS typically water, and the article or object to be cleaned
ls brought into contact with the washing medium. In general,
the washing medium will have a pH adjusted to within the
range of pH8 to 12. It will be recognised that washing
compositions according to the l)resent invention are suitable
for dissolution or incorporation in any aqueous medium.They
are particularly suited to dissolution or incorporation ln
aqueous media containing a significant concentration of
magnesium ions. In consequence, it will be seen that they
are suited to dissolution or incorporation in a very wide
xange of aqueous media. The article or object to be washed
can be any article or object currently so washed by
conventional washing compositiorls. An illustrative list of
such objects or articles comprises textile materials
..
,.. .
: : .. ' : ` . . . . -
'' '. ` ; " `' . - ' ~' ` '"` ~ ':,. :
. . , ` , . ' . ', .
,- - :~
,:
GC76
1~1471~
including both natural and synthetic materials such as
cotton, linen, polyamides, polyesters, polyacrylonitriles,
polyurethane and polyvinylchloride, and hard surfaces such
as walls, floors, work surfaces, and household and industrial
objects made of wood, plastic, metal, glass, stone or
ceramics.
, .. ., . _ . , , _ . _ _ _ _
The washing compositions are normally incorporated
in aqueous media in amounts of from 0.5 to 20 gpl, frequently
from 1 to 10 gpl, giving in many cases a builder concentration
in the range of 0.3 to 6.o gpl. The washing process is
normally carried out at a temperature of from ambient up
to 100C, and frequently from 30 to 90C.
~aving described the invention in general terms, the
specific embodiments are disclosed hereinafter by way of
example only,in which amounts and weight ratios of zeolites
are shown on an anhydrous basis.
Exam~le 1
In this Example water containing 100 ppm total hardness
in a 1:1 by welght ratio of calcium to magnesium was softened
by the addition of 0.45 gpl of either 13X/4A mixture in the
weight ratlos indicated in Table 1, or (by way of comparison
only) with solely 13X or 4A, Y or mordenite at 25C. Samples
were taken after a half or one minute and ten minutes and
analysed for calcium and magnesium. The results, expressed
as the percentage of calcium, magnesium and total hardness
which have been removed from the water, are summarised in
Table 1 below.
- 20
~. . . . . . : ..
'
.
GC76
.,
1~1L14'7:~
. .
TABLE I
_ Hardness Removal
13X/4A Tim~
Zeolite wk ratio Minutes % Ca % Mg % Total
. ., _ _ __
13X/4A 1:3 1 89 43 66
. 13X/4A 1:3 10 97 S0 73
13X/4A 1:1 1 77 49 63
13X/4A 1:1 10 90 70 80
13X~4A 3:1 1 89 65 77
0 13X/4A 3:1 10 95 76 85
13X 1 80 71 75
13X lo ~4 79 81
4A ~ 70 8 39 . :
4A 10 96 17 57
Y ~ 48 30 3
Y 10 57 41 49 -~
mordenite ~ 32 13 22
" . 10 36 25 31
From Table I, lt can be seen that the optimal total hardness .
~0
removal occurred using a mixture containing 75% zeollte I3X,
.
not only after one minute but also after ten minutes. :
ExamPle 2
In thls Example, a simllar procedure to that of
Example 1 was followed, except that the water employed
contained 250 ppm total hardness, agaln ln a 1:1 by welght
ratlo of calcium to magneslu~, and 1.6 grams per lltre
of zeollte or zeolite mixture was added to remove the :
- 21 -
, . . .
,
' ' ,'' ' ' '" ' ~'.' '' ."' ''. ' '' ~'.''' ', . ,
.'
magnesium and calcium ions. The result is summarised in
Table II below~ _ ..... ..
TABTE II
..... _
Hardness Removal
S Zeolite 13X/4A Ti.me l _ ..
wt ratio Mimltes % Ca % Mg X Total
.- , .. , .,
. 4A 1 97 16 56
4A . 10 97 29 63
10 13X/4A 1:3 1 94 34 64
13X/4A 1:3 1~ 98 56 79
13X/4A 1:1 1 95 34 64
13X/4A 1:1 lo 97 81 89
13X/4A 3:1 1 96 87 91
15 13X/4A 3:1 10 99 93 96
13X 1 94 87 90
13X 1~ 96 90 93
. . ..
. Exam~le 3
In this Example, water having a total hardness content
of 250 ppm in an 3:1 weight ratio of calcium to magnesium
was softened by the addition of 5gpl. of a heavy duty
detergent composition comprising sodium linear alkyl benzene
sulphonate 8%, sodium carboxymethyl cellulose 1%, sodium.
sulphate 10%, sodium perborate tetrahydrate ~5.%, eeolite
or zeolite mixture 32X, misce:Llaneous 0.5% and the balance
sodium sulphate and wa.ter. The results are summarised in
T~hl~ III bel~
- 22 - -
: '''''' ' :
.
GC76
TABLI-. III
. . _ _
Hardness Removal
Zeolite 13X/4A Time .
wt ratio Minutes ~ Ca % Mg % Total
5 4A 1 ~4 28 61
4A 1~ 95 29 79
13X/4A 1:3. 1 ~2 S0 71
13X/4A 1:3 1~ 95 57 86
13X/4A 1:1 1 92 64 78 .
1013X/4A 1:1 1(l 94 64 87
13X/4A 3:1 1 92 64 78
13X/4A 3:1 1() 94 79 90
13X 1 90 64 77
lS13X 1~ 91 71 87
From Table III it can be seen that again, ëvën ~n the
presence of sodium salts, the mixture which removed total
hardness best was that contair'ing 75% 13X and 25% 4A.
- Exiample_4
In this Example, Example 3 was repeated, except that
the detergent composition was used at a concentration o~ :
8.5 gpl. The results are su~lmarised in Table IV.
. --
. . - 23 - .
. -.. - . . . . - - .: " ~ . - . . -
~- . .: .. : .
. . . : , . . -: - , ,- .
- ; . . : .. ., ~ . - - .: -
.,: ,. : ,, .. :
.. - :.: ...... : . ~
: . : . . . .... ... .. .
,. ,.' ' ' .': ' . ~ :, ,
- . - . . ~ , :.~ . : . . .
... ., :
-,, , .. . ~ .
GC76
~14'~1~
TAsL~ IV
. _ ~ ,
13X/4A Time Hard~ less Remov
Zeolite wt ratio Minutes % Ca X Mg % Total
_ . . . _ _
4A 1 96 40 68
4A 10 96 50 81
13X/4A 1~3 1 93 76 84
13X/4A 1:3 10 98 80 90
10 13X/4A 1:1 1 95 85 90
13X/4A 1:1 lo 95 85 92
13X/4A 3:1 1 93 85 89
13X/4A 3:1 lo 95 85 92
13X 1 93 85 89
13X _ 10 94 9o 93
From Table IV it will be seen that water is softe~ed rather
more rapidly than whqn the lower concentration, as in
Example 3, i9 used. It will also be noted that under these
conditions, a relatively high weight ratio of zeolite to
hardness, the mixtures containing 50X or more 13X, behaved
very similarly not only as to the rate at which the hardness
- was removed, but also to the extent to which removal
occurred.
- ~ , , .
:- ;. . ," ' :
' . ' . . ~ '
.: .. . .. ~ :. . . .
... . .
r o
~9L7~
Exam~le 5
In this Example,washing compositions were prepared
comprising:-
_
ComPOnent wt %
Sodium llnear alkyl benzene sulphonate 8
Sodium perborate tetrahydrate 25
Sodium silicate 9
E.D.T.A l
SudR Suppressor 3
._ .~ . . .... . .
Builder 35
Sodium sulphateJwater balance
, ' 15 .
_ .
In order to determine its washing abilityj the
compos1tion of Example 5 (Ex 5) was compared with an
otherwise identical composition Cl, the builder of Ex 5
comprising zeolite mix, 13X:4A of 3:1 anhydrous by wt.
32%, glassy phosphate, Na4P207(P03)3 2% and diethylene-
triaminepenta (methylenephosphonic acid) 1% and that of
comparison Cl comprising entirely codium tripolyphosphate.
The suds suppressor was saponi~ied hydrogenated marlne
oil fatty acid, in all compositions. The washing perfor~ance
.
of the two compositions were compared in the following way. Loads
- 25 -
. . , . , , .. .: . , .. ,: . , ... . . . . - .: . , . .. , - . . . . . . . .
.. . . :. . .. - - , - : . - . . .
. .: : . : : :- ... - , - . . . . . . .
.
- : . - ... . . . . - ~ - . . -
... .. . ~ : -
.. . ..
GC76
7ia
of fabrics were made up from artificlally stained and aged desi~ed
white cotton swatches and items that had been soiled in
normal domestic usage. In order to make the comparison as
falr as possible, efforts were made to distribute the ltems
such that the load washed by the invention composition was
similar as regards composition and degree of solling to the
load washed by the comparison composition. The loads were
washed in domestic automatic washing machines, employing
a pre-wash at 40C and a main wa~h at 90C and both using
105g washlng compositlon in 20 litres of water. The water
hardness was 14 German hardn~ss equivalent to 250ppm
measured as CaC03, in which the mole ratio of calclum to
. . . , , . _ . , _ , _ _ , .
magnesium was 3:1. The artificially stained swatches after
washing were compared u ing an Elrepho reflectometer commercially
available from Karl Zeiss, operated under simulated natural
daylight conditions, and under simulated natural light by a
panel of non-colour blind judges. The views of the panel as
to stain removal were then statistically evaluated using the
4 point Scheffe preferance scale, and analy~ed on a 95%
probability basis. The results obtained are show,n in Table 5,
in whlch a posltlve score for the mean difference indicates
that the first product was preferred to the second product
and a negative score indlcates that the seaond product was
preferred. The asterlsk indicates that the mean difference
was significant to at least 95~ conf~dence level, when it
appears in Tables 5, 6, 7 and 10.
- 26
.
.. .. . . . ,. ", . , -, .. ..
- . . . . . . .
. ,
- : . . ,- - - : ., . ~ . . .
... . .- . -
. i - , . .. .- .
: .
. .,' . '. '. .. - : . ~ ,. ' - .:: .'
.. . . . . :
- ~ , . . .
.
GC7~
.
7~L~
_ . , .. _ _ . . _ .. _ . .. .
TABLE 5
. _.
Cl v Ex.
Stain
Mean Difference Yardstick
~ea -2.84* 0.98
Red Wine -0.34 1.56
Cocoa -1.38 1.48
Blood/Milk/Ink -2.0* 1.52
Mud -1.22 1.54
1~ Cocoa (milky) -1.44 1.94
Make-up ll.~ ~.86
_ , . ...
From the above, lt can be seen that except in the case
o~ make-up, the composition accordlng to the invention Ex S
produced better stain removal, as judged by the panel. The
... , . _. . _ . __ _
difference i8 especially marked ln the case o~ the tea and
the combined blood/milk/ink stalns, in both cases being
well beyond the point at which on a 95% probabilit~ the
. dlfference was significant. It will be also notlced that
in the case of cocoa and mud the mean di~ference was
approachlng the point at which it would become significant
at the 95% probability. From the above results, it can be
concludcd that on balance the composition according to the
present invention i8 better than the comparison washing
- 25 composition which contained as detergent builder sodium
tripolyphosphate.
Example 6 . .-
In this Example, the washing composition Ex 6.was.identical
to that in Exa~ple 5 except that 2% by weight o the
~ 27
- , . . . - ~ , . , . .. . ~ ..
..
-. ,. . . . . . ~. . .. . ~ .
... . , . . - : : ~
GC76
71~)
sodlum salt of poly(alpha-hydroxyacrylic acid) was employed
instead of 1% of diethylenetriaminepenta (methylenephosphonic
acid~. One again, it was compared with a comparison washing
composition C2 which was the same as Cl, but with the inclusion
of an extra 1% of sodium tripolyphosphate. The comparison was
effected in the same way as ln Example 5 and the results
obtained were as follows :-
TABLE 6
C2 v E~ 6
Stain Mean DlfferenceYardstick
Make-up -0.66 0.72
Cocoa (milky) +0.38 1.18
Mud ~0.34 1.82
Tea -1.44* 1.04
Red Wine -0.56 0.66
Cocoa ~0.56 1.68
Blood/Milk/Ink +0.34 0.72
_
From the above results, it will be seen that there was
only one stain ln whlch the difference detected was
significant at the 95% confidence level. The result was
in favour of the composition according to the present
invention, Ex 6 as were results for two addltional stains which
very closely approached the 95% confidence level, namely
tho3e ln respect of make-up and red wlne~ Although for the
other ~tains, the comparison composition C2 was preferred,
- - , . : : . : : . : . .
:
.
GC76
.
the mean dlfference was only 18~, 32%, 33% and 47%
re~pectively of the yardstick, i.e. a much smaller
difference than would be required for the difference to
be significant at the 95% confidence level. From the
above results, therefoxe, it can be seen that the invention
composition at least matches on average the comparlson
composition.
.... _ .
Exam~le 7
In thls Example, the wa-~hing composltion Ex 7 was
ldentlcal to that of Example 5, but employlng 2% instead of
1% by weight of the diethylenetrlaminepenta
(methylenephosphonic acld). Two compari~on compositions were
prepared containing the same amount of sodium linear alkyl
benzene sulphonate, 8%, sodium perborate tetrahydrate, 25%,
sodium sllicate, 9%, EDTA, 1%, sud suppressor, 3%, and as
builder, either Zeolite 4A or sodlum tripolyphosphate, 32%,
and the balance water. The 4A zeolite-containing aomparison
18 designated C3z and the tripolyphosphate-containing
composition C3P.
The washlng performance of the compositionC were
- tested using the test method dlsclosed in Example l, but
employing soft water havlng a hardness of 5 expressed as
German hardness and approximately 83ppm expressed as CaC03.
The results are summarised in Table 7
~ .
': , ' ' ; '~
' ' ~,
GC76
.,
TABLE 7
.. . _ . . .. ,, . . . , _ . ... . . . _ _
.
C3Z v Ex.3C3P v Ex.3
Stain Mean D~fferenceMean Difference
_ .
Blood/Milk/ink -0.86* -1.33*
Red Wine -0.85 -0.65
Cocoa -1.17* -0.96*
Tea -1.87* -0.44
Gravy ~0.07 -0.32
Mud -0.08 ~0.08
Chocolate Pudding +0.04 +0.02
Make-up +0.02 -0.71*
From the above results lt can be seen that the inventlon
composltion matched both the prlor axt compositions ln respect
of all stains ~figures of +0.04 and +0.02 have no significance)
and was markedly superlor in respect of several stains, in
- partlcular tea, cocoa, red wlne and blood/milk/ink. Thus, on
balance, the compositlon Ex.7 was better than comparable
composltlon6 C3Z and C3P.
Example 8
In thl~ Example the effectiveness of mlxtures of zeollte
to sodlum trlpolyphosphate (STPP) ln a weight ratio of 90:10
at removing hardness from water at 25C wa-R measured. The
total hardness was 250 ppm of calclum and magneslum in a
welght ratio of 1:1 and the bullder mlxture used at 1.5 gpl
concentration. The xesults are summarlsed ln Table 8 below,
re6ults ~or 13X/STPP and 4A/STPP mlxe~ being present for
_ 30 _
,, , ,
.. . , , - .. :. .. . , ~.... . ....
,. ... : . . . '' ' ~ ' -
: . .
~' - , '
' '
"' ~,
GC76
_~ ,
7i~
comparlson only, and the 13X/4A/STPP mix having a weight
ratlo of 13X to 4A of 3:1 demonstrating the lnvention, and
show the proportion of hardness removed by the zeolite
portion of the builder mix.
TABLE 8
~ Ca % Mg % Hardness % Nardness
Mix Removed Removed RemovedRemalning After
All STPP Used
2min lOmin 2min lOmln 2mln lOmln
,
4A/STPP 89 89 26 43 58 66 18
13X/STPP 80 80 54 54 67 67 17
15 Mlx/STPP 82 88 54 60 68 74 10
.. .
.. .. , , _ _ _ _ _ , . .. _ _ ... .. _ _ .... .
From $able 8 it can be seen that not only wa~ the
13X/4A/STPP mlxture ~lgnlficantly the best at hardness
removal, the hardnes~ remalnlng after all the STPP was used
ao up waa much the lowe~t ln the case of the 13X/4A4STPP
mlxture.
Example 9
In this Example, a similar procedure to Example 8 was
followed, dlffering only by use of a 50/50 mix o zeolite/STPP,
25 and mea~urlng the amount of free STPP remalning in solution
after 10 minutes. The results are summarlsed ln Table 9,
13X/STPP and 4A/STPP belng present by way of comparison only.
~he Mlx/STPP contalned 13X, 4A and STPP in a welght ratio of 3:1:4.
~ 31
- ~,
'' 1.
' ' '' .. '.
~ . .
GC76
~:~14~1~
TABLE_9
__ % Ca % Mg ~ Hardness % Free STPP
Mix Removed Removed Removed Remaining After
2min lOmin 2mln lOmn 2min lOmin lO mln~
. .. . . .
4A/STPP 42 40 3 3 23 22 4.3
13X/STPP 32 35 3 3 18 l9 0.0
Mlx/STPP 35 46 6 14 2l 30 14.1
.. . . , . .. . . . .. _ . .. ... __ . . .
From Table 9 lt can be seen that the proportion of
hardness removed by the zeollte portion of the bullder mix
has fallen from when lt comprised 90~, but again after lO
mlnutes the Mi~/STPP has removed a greater proportion of
the hardness than has elther the 13X or 4A zeolltes, and that
very slgniflcantly a substantlal amount of STPP stlll remain~
ln ~olutlon a~ter 10 mlnutes, whlch would be free to perform
the other useful functions of STPP, such as soll suspenslon.
Exam~le lO
. In thls Example, the washlng performance of compositions
was compared by the method descrlbed ln Example 5. The
components of the composltions in this Example were the same
and ln the same amounts as in the composltion of Example 5
except that the builder ln composltion Example 10 was a
13X/4A/STPP mlxture ln a welght ratlo of 3:1:4 and in
the comparlson composltlon C4 was a 4A/STPP mixture ln a
weight ratlo of 50:50. The result~ of the washing trials
are summarlsed ln Table lO below.
- 32
~, . - . .
.
~ . . .. . . .
.. . . . , .~ .. ..
.. . .- . : . . . . .
. . . .~. , .:
. : ..
,- . ~ . . -, . . .
.
GC76
TABLE 10
. . . _ ,
Stain C4 v Ex.10 Yardstick
Mean Difference
. _ . . ... ,
~lood/Milk/Ink -2.66* slgnificant 1.03
Tea 0.42 1.26
Cocoa -1.76* slgnificant 1.12
Dirty Motor Oil-0.26 1.32
Make-up -0.34 O.56
Mud 0.26 1.32
- From Table 10 it can be seen that overall the Example
composition was adjudged to be better than the comparlson
product at cleansing the varlous soil~.
,
,
- ~ 33
-
. - : .-', ~ :
- . - . : , : ~ .
.
::
